title: Monolayer properties of 1,3-diamidophospholipids.
abstract: While nature provides an endless variety of phospholipids presenting hydrolyzable ester linkages for the 1,2-positioned hydrocarbon tails, we designed and synthesized 1,3-diamidophospholipids which contain stable fatty acid amides. These new phospholipids form faceted unilamellar vesicles with mechanosensitive properties. Aiming to understand the mechanism responsible for this behavior at a molecular level, we investigated the 1,3-diamidophospholipid family in monolayers, a simplified model membrane system. Langmuir isotherms combined with in situ grazing incidence X-ray diffraction (GIXD), specular X-ray reflectivity (XR), and infrared reflection-absorption spectroscopy (IRRAS) allowed the characterization of the monolayers from a structural and thermodynamical point of view. The existence of strong headgroup interactions due to the formation of a hydrogen-bonding network was clearly revealed by IRRAS and by the high rigidity of the monolayers. GIXD showed that only the longer chain compounds of the series (Pad-PC-Pad (1,3-dipalmitamidopropan-2-phosphocholine) and Sad-PC-Sad (1,3-distearamidopropan-2-phosphocholine) were able to form ordered monolayers. The chains are strongly tilted in a rigid lattice formed due to these hydrogen-bonding interactions between the headgroups. The thermodynamical analysis leads to a critical temperature of the monolayer which is clearly different from the main phase transition temperature in bulk, indicating that there must be a different structural arrangement of the 1,3-diamidophospholipids in monolayers and in bilayers.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Quai Ernest-Ansermet 30, 1211 Geneva, Switzerland.
authors.forename: Lllya A
authors.initials: LA
authors.lastname: Fedotenko
authors.forename: Cristina
authors.initials: C
authors.lastname: Stefaniu
authors.forename: Gerald
authors.initials: G
authors.lastname: Brezesinski
authors.forename: Andreas
authors.initials: A
authors.lastname: Zumbuehl
mesh_terms: D000577:Amides / Q000737:chemistry*; D010743:Phospholipids / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D014961:X-Ray Diffraction
chemical_list: D000577:Amides; D010743:Phospholipids